Viscose spinning solution



Patented Oct. 11, 1938 UNITED STATES PATENT OFFICE vrscoss srmnmc SOLUTION Rudolph 8. Bley, Elizabethton, Tenn, asaignor to North American Rayon Corporation, New York, N. Y., a corporation oi Delaware No Drawing. Application December 2, 1937, Serial No. 177,825

ting bath (spin bath) However, since the introduction of the viscose process great troubles'have been and are still experienced as far as continuous spinning is concerned due to impurities, such as, for example, precipitated cellulose parln ticles, sulphur and resin particles, zinc compounds, etc., present in either the viscose solution .or the spin bath. These impurities gradually contaminate the spinnerets, clog and reduce 'the widths of the spinneret holes with the result that 15 filaments of uneven thicxness are obtained. If

the contamination of the'spinnerets and the clogging of their holes proceeds the individual filaments start to tear and occasion interruption of the spinning process.

20 By experimentation, I have found that the .contamination of spinneretsand the clogging of spinneret holes may be overcome by spinning viscose solutions in the presence of cation-active compounds, these compounds being produced by con- 25 densing a halogenated petroleum or a halogenatedpetroleum constituent containing at least one hydrocarbon having a chain of eight or more carbon atoms with an organic sulphide, selectedfrom the group consisting of dialkyl sulphides, 0 diaryl sulphides and alkyl-aryl sulphides under substantially anhydrous conditions.

Petroleum consists of complex mixtures of hy- -drocarbons concerning the cheinical nature of which there is very little information, although 35 there are indications that all of these materials contain members of the methane series, the polymethylene series and the benzene series of hydro carbons. The difference between petroleums of various sources resides in the proportions of the 40 difierent types of hydrocarbons and in the chemical nature and amounts of their impurities. Pennsylvania oil, for example, contains a large proportion of methane hydrocarbons and practically no impurities of sulphur or nitrogen compounds. About thirty hydrocarbons have been isolated and identified withcertainty. Distillation is the principal method in separating petroleum into useful components. The distilled frac- 50 tions from crude petroleum are casinghead gasoline, gasoline, kerosene, gas oil and lighter lubricating oils (neutrals). The residues from such distillation supply most of the lubricating oils (bright stock), petrolatum in pasty or liquid form and either paraflln wax or petroleum pitch,

depending upon the nature of the crude petroleum. Kerosene is any mixture of hydrocarbons which is not volatile enough for use in explosion motors. Cracked gasolines are rich in olefins and dioleflns. Paraiiin wax was originally obtained from tars from the distillation of wood,

peat, and lignite, but is now obtained from petroleum, and especially from Pennsylvania parafllnbase oils. Little information is available about the composition of paraffin waxes except that it consists mainly of higher alkanes and only small amounts of the normal compounds. Petrolatum (Vaseline) is. a pasty mixture of hydrocarbons similar to paraflin while liquid petrolatum is a high boiling petroleum distillate. Ozokerite is a natural paraflln wax originating in Galicia; in bleached form it is termed "ceresin. All or these petroleum hydrocarbons may be halogenated in conventional manner in the presence or absence of catalysts to form halogenated hydrocarbon mixtures adapted to be condensed with the tertiary bases and organic sulphides, set forth above. The materials, 1. e., crude petroleums, gasolines, ,kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paramn waxes, to be halogenated may first be dissolved in carbon tetrachloride, etc., and subsequently chlorine, bromine, etc., in gaseous form introduced therein until the heat of reaction abates. Halogenated' compounds, containing about 25 to 40% of halogen may be obtained in this manner. However, upon prolonging the introduction of halogens, compounds may be obtained containing up to about 75% of a halogen, and it is to be noted that the boiling or fusing points of the raw materials are either lowered or raised by halogenation. Hydrochloric acid, hydrobromic acid, etc., formed during this reaction must be removed, preferably by neutralization. Catalysts, such as iron, etc., may be added to the mixtures to accelerate halogena? tion. Halogenation will also proceed more rapidly by carrying out the reaction under the influence of ultra-violet rays. The halogenation may also be performed in accordance with processes disclosed, for example, in U. S. Patent #989,225 to Blakeman of April 11, 1911; U. S. Patent #1,246,810 to Ellis of November 13, 1917.; U. S. Patent #l,432,76l to Kock of October 24, 3922; etc. Chlorinated paraffin wax, sold under the trade name of Chlorafin is a very suitable raw material for my process.

Organic sulphides capable of being condensed with the halogenated, hydrocarbonaceous materials set forth above are dialkyl sulphides, diaryl sulphides and alkyl-ary sulphides, having the following structuri 7 in which R1 and R: represent monovalent aliphatic 'ialkyl) or aromatic (argl) radicals. Examples of such organic sulphides are dimethyl sulphide, diethyl sulphide, methyl-ethyl sulphide, methyl-propyl sulphide; dibutyl sulphide, methylbenzyl sulphide, propyi-ethyl sulphide, dibenzyl sulphide, diphnyl sulphide, etc.

Thus; by condensing an organic sulphide with a halegenatedg hydrocarbonaceous material hf the aforementioned group, sulphonium halides are obtained, having the structure:

pounds which carry in the anion a more orfless extended hydrocarbon chain (fat chain). They flocculate in neutral '(salt); alkaline and acidic aqueous solutions, and also hard water. Com- I mon soaps, sulphonated oilsfsalts of sulphonated fatty acids, etc., are examples of anion-active compounds,"and,the'y are unable to prevent the incrustation of spinnerets and spinneret holes. These incrdstation inhibitors are prepared by heating a halogenated hydrocarbonaceous ligaterial selected from the group consisting of crude petroleumsjgasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums, and paraffin waxes with an organic sslphide at a moderate temperaturepreferably under reflux-until condensation is completed. Before heating the two, components they may be dissolved in a suitable,

inert solvent, such as, for example, benzene,

ether, toluene, etc; i. e., in solvents which are incapable of chemically reacting with thelicompounds to 'be condensed. The inert solvent may subsequently by removed from the condensation products by distillation, and the unreacted sulphide may be separated from the condensation products by distiila'tion, extraction, etc. The crude incrustationilnhibitors may contain :a number of difierent condensation products which need not be separated from each other. In other words, the crude condensation products' (incrustation inhibitors) containingcations-active .and cation-inactive constituents may, for reasons of economy, be added without further purification to viscose solutions or spin baths (setting baths). Although these cation-active halides, i. e., bromides, chlorides, iiodides and fluorides, may form sulphonium bases in viscose solutions and sul-; phonium salts in acid spin baths, they retain; their surface-activity and, thus, their property of preventing incrustation. If very small amounts 7 of these condensation products are added. to viscose solutionsor spin baths the physical characteristics, such as strength, plasticity, lustre, etc.,

of regenerated cellulose produced therefrom or therein, respectively, remain practically unaltered. Upon increasing the amount of incrustationinhibitor in a given viscose solution or spin bath, the regenerated cellulose produced therefrom or therein, respectively, may alter its physical characteristics, 1. e., it may acquire a soft lustre, become moreplastic, iose part of its original strength, etc. Ear such reasons, the amounts of such coinpounds to be added to viscose solutions or spinf baths control the physical properties of the finished cellulosic products. words, these additions are critical and their amounts must be predetermined by experimentation. Additions of about 0.3 to 1.0 gram per liter In other of viscose or spin bath are insuificient to sub- Ethyl-methyl sulphide is condensed with a halogenated, hydrocarbonaceous material selected from the group consisting of crude petreleums, kerosenes, gasolines, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes by heating under reflux until condensation is completed. About 0.4 $011.0 gram of the condensation products are added to one liter of a viscose solution of conventional cellulose content and maturity. This solution is then spun into ,7 a conventional, acid spinbath, such as, for exf ample, a? glucose bath, a magnesium-zinc bath, etc. ,The spinnerets and spinneret holesremain cjean on prolonged spinning in comparison with the spin bath free from cation-active compounds. Any dialkyl sulphide, diaryl sulphide or alkylaryl sulphide may be used in the condensation, which may be carried out at any temperature at which the two *reactants and the sulphonium halide remain stable. I

Example II i An-alkyl-aryl sulphide, a dialkyl sulphide or a diaryl sulphide, such as, for example, dibenzyl sulphide is condensed with a halogenated paraflin wax in the presence of 'an inert solvent, such as;

'for example, benzene, 'etc., under substantially anhydrous conditions. A conventional viscose solution is extruded through fine orifices of a spinneret of a precious metal into an acid spin bath, this bath'containing sulphuric acigl, sodium ff sulphate, ammonium sulphate and zinc-i sulphate plus about 0.05% by weightcf a cation-active substance set forth above. Spinning irregulari ties and difficulties are substantially overcome while 'without this infiibitor spinning is interrupted after ajvery short period of time. These inhibitors are Qespecially suitable for continuous spinning processes using sulphuric acid-zinc sulphate Toaths. These sulphides may be condensed with any halogenated, hydrocarbonaceous material of the group set forth above.

Example II;

Cation-active condensation products are added to both the viscose solutions and the spin baths cation-active condensation product of a haloto allow continuous formation of lustrous or softlustre viscose products.

Although these examples will serve to illustrate the present invention, I do not wish to be limited to the inhibitors and concentration thereof recited therein, since I may use any cationactive sulphonium compound of the group set forth above and vary the physical characteristics of regenerated cellulose by varying their amounts in viscose solutions and/or spin baths, provided these inhibitors are sufficiently soluble in viscose solutions and/or spin baths to furnish' cations therein.

Modifications of my invention will readily be recognized by those skilled in the art, and I desire to include all such modifications and variations coming within the scope of the appended claims.

I claim:

1. A spinning solution for the manufacture of artificial products comprising a viscose solution and a cation-active condensation product of a.

halogenated hydrocarbonaceous material selected from the group consisting of halogenated crude petroleums, halogenated gasolines, halogenated kerosenes, halogenated lubricating oils, halogenated pasty petrolatums, halogenated liquid petrolatums and halogenated paraffin waxes and an organic sulphide selected from the group genated hydrocarbonaceous material selected' from the group consisting of halogenated crude petroleums, halogenated gasolines, halogenated kerosenes, halogenated lubricating oils, halogenated pasty petrolatums, halogenated liquid petrolatums and halogenated parailin waxes and an organic sulphide selected from the group. consisting of dialkyl sulphides, alkyl-aryl sulphides and diaryl sulphides, said condensation product being sufliciently soluble in said viscose solution to become cation-active therein.

4. A spinning solution for the manufacture of artificial products comprising one liter of a viscose solution and about 0.4 to 1.0 gram of a genated parafiin wax and ethyl-methyl sulphide.

5. A soft-lustre regenerated cellulose containing a finely divided cation-active condensation product of a halogenated hydrocarbonaceous ma terial selected from the group consisting of halogenated crude petroleums, halogenated gasolines, halogenated kerosenes, halogenated lubricating oils, halogenated pasty petrolatums, halogenated liquid petrolatums and halogenated paraflin waxes and an organic sulphide selected from the group consisting of dialkyl sulphides, alkyl-aryl Y sulphides and diaryl sulphidesin a sufiicient amount to diminish the lustre thereof.

' artificial products comprising a viscose solution and a cation-active condensation product of a I chlorinated paraflin wax and a dialkyl sulphide, said condensation product being sufficiently soluble in said viscose solution to become cationactive therein.

9. A spinning solution for the manufacture of artificial products comprising one liter of a visproduct of a chlorinated paraffin wax and ethylmethyl sulphide in a suflicient amount to diminish the lustre thereof.

12. A soft-lustre regenerated cellulose contain- 7 ing a finely divided cation-active condensation product of a chlorinated paraflln wax and a dialkyl sulphide in a suflicient amount to diminish the lustre thereof. v

RUDOLPH S. BLEY. 

